WO2010094417A1 - Dispersions de polyuréthane-polyurée fonctionnalisées - Google Patents

Dispersions de polyuréthane-polyurée fonctionnalisées Download PDF

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Publication number
WO2010094417A1
WO2010094417A1 PCT/EP2010/000801 EP2010000801W WO2010094417A1 WO 2010094417 A1 WO2010094417 A1 WO 2010094417A1 EP 2010000801 W EP2010000801 W EP 2010000801W WO 2010094417 A1 WO2010094417 A1 WO 2010094417A1
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WIPO (PCT)
Prior art keywords
polyurea dispersions
functionality
dispersions according
aqueous polyurethane
isocyanate
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PCT/EP2010/000801
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German (de)
English (en)
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WO2010094417A8 (fr
Inventor
Hans Georg Grablowitz
Thomas Feller
Thomas Michaelis
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Bayer Materialscience Ag
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Priority to US13/147,254 priority Critical patent/US8513334B2/en
Priority to CN201080008282.XA priority patent/CN102325816B/zh
Priority to ES10703236T priority patent/ES2400415T3/es
Priority to EP10703236A priority patent/EP2398835B1/fr
Priority to JP2011550454A priority patent/JP5542846B2/ja
Publication of WO2010094417A1 publication Critical patent/WO2010094417A1/fr
Publication of WO2010094417A8 publication Critical patent/WO2010094417A8/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0828—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing sulfonate groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/2845—Monohydroxy epoxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
    • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/721—Two or more polyisocyanates not provided for in one single group C08G18/73 - C08G18/80
    • C08G18/722—Combination of two or more aliphatic and/or cycloaliphatic polyisocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group

Definitions

  • the present invention relates to aqueous polyurethaneurea dispersions having incorporated functional groups and coating compositions prepared therefrom, a process for their preparation and their use for the preparation of coating compositions.
  • Coatings based on polyurethane dispersions come in different applications, such as e.g. the textile coating, plastic, automotive painting or glass fiber coating used.
  • Functionalized polymers for coatings generally offer the possibility in a further process step to carry out polymer-analogous reactions in order to improve the properties of the coating. It is often attempted to achieve a high molecular weight, since a high molecular weight is generally positive for the final properties of the coating, such as e.g. the solvent stability and hydrolysis resistance.
  • US Pat. No. 6,586,523 describes self-crosslinking polyurethane dispersions which consist of hydroxy-functional polyurethanes whose isocyanate groups are partly blocked.
  • a disadvantage of the polymers described therein is that the use of elevated temperatures releases the blocking agent, which is undesirable in terms of occupational hygiene.
  • the object of the present invention was thus to provide self-crosslinking, aqueous polyurethaneurea dispersions which can be processed into coatings having a very good resistance to hydrolysis.
  • epoxy-functional polyurethane polyureas can be thermally crosslinked without the addition of further compounds (single-component (LC) system) or crosslinked by addition of polyfunctional crosslinkers such as polyamines and / or polyisocyanates (two-component (2K) system). Furthermore, the coating compositions prepared from the polyurethane-polyurea dispersions according to the invention show excellent hydrolytic stability.
  • the present invention thus provides aqueous polyurethane-polyurea
  • R '" H, CH 2 CH 2 SO 3 " , CH 3 , CH 2 CH 3 , cyclohexyl, CH 2 CH 2 OH.
  • the polyurethaneurea dispersions of the invention contain as structural components
  • the polyurethaneurea dispersions according to the invention contain this
  • component a From 5 to 40% by weight, preferably from 10 to 35% by weight, particularly preferably from 15 to 25% by weight, of component a),
  • component c optionally 0 to 5 wt .-%, preferably 0.5 to 4.0 wt .-%, particularly preferably 1 to 3 wt .-% of component c),
  • component g 0.5 to 15 wt .-%, preferably 1 to 12 wt .-%, particularly preferably 2 to 10 wt .-% of component g).
  • Suitable polyisocyanates a) are the aromatic, aromatic, aliphatic or cycloaliphatic polyisocyanates known per se to the person skilled in the art.
  • Suitable polyisocyanates a) are e.g. 1, 4-butylene diisocyanate, 1, 6-hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI), 2,2,4- and / or 2,4,4-trimethylhexamethylene diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl ) methanes or mixtures thereof of any isomer content,
  • Proportionally also polyisocyanates with a functionality> 2 can be used. These include modified diisocyanates having uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures, as well as unmodified polyisocyanates having more than 2 NCO groups per molecule, e.g. 4-Isocyanatomethyl-l, 8-octane diisocyanate (nonane triisocyanate) or triphenylmethane-4,4 ', 4 "-triisocyanat.
  • modified diisocyanates having uretdione, isocyanurate, urethane, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures as well as unmodified polyisocyanates having more than 2 NCO groups per molecule, e.g. 4-Is
  • polyisocyanates or polyisocyanate mixtures of the abovementioned type with exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups having an average functionality of 2 to 4, preferably 2 to 2.6 and more preferably 2 to 2.4.
  • Polymeric polyols which can be used as compounds b) have a molecular weight M n of from 400 to 8000 g / mol, preferably from 400 to 6000 g / mol and more preferably from 500 to 3000 g / mol.
  • Their hydroxyl number is 22 to 400 mg KOH / g, preferably 30 to 300 mg KOH / g and more preferably 40 to 250 mg KOH / g and have an OH functionality of 1.5 to 6, preferably from 1.8 to 3 and more preferably from 1.9 to 2.1.
  • Polyols b) for the purposes of the present invention are the organic polyhydroxyl compounds known in polyurethane coating technology, such as the customary polyester polyols, polyacrylate polyols, polyurethane polyols, polycarbonate polyols, polyether polyols, polyester polyacrylate polyols and polyurethane polyacrylate polyols, polyurethane polyester polyols, polyurethane polyether polyols, polyurethane polycarbonate polyols, polyester polycarbonate polyols, phenol / Formaldehyde resins, alone or in mixtures. Polyester polyols, polyether polyols or polycarbonate polyols are preferred, polyester polyols are particularly preferred.
  • polyether polyols e.g. the polyaddition products of styrene oxides, ethylene oxide,
  • Suitable hydroxy-functional polyethers have OH functionalities of from 1.5 to 6.0, preferably from 1.8 to 3.0, OH numbers of from 50 to 700, preferably from 100 to 600 mg KOH / g solids and molecular weights M n of from 400 to 4 000 g / mol, preferably from 400 to 3500, such as alkoxylation of hydroxy-functional starter molecules such as ethylene glycol, propylene glycol, butanediol, hexanediol, trimethylolpropane, glycerol, pentaerythritol, sorbitol or mixtures of these and other hydroxy-functional compounds with propylene oxide or butylene oxide.
  • Preferred polyether component b) are polypropylene oxide polyols and polytetramethylene oxide polyols having a molecular weight of from 400 to 4000 g / mol.
  • the particularly low molecular weight polyether polyols can be water-soluble at correspondingly high OH contents.
  • water-insoluble polypropylene oxide polyols and polytetramethylene oxide polyols having a molecular weight of 500 to 3000 g / mol and mixtures thereof are particularly preferred.
  • polyester polyols b) are the on are the known polycondensates of di- and optionally tri-and tetraols and di- and optionally tri- and tetra) carboxylic acids or hydroxycarboxylic acids or lactones.
  • free polycarboxylic acids it is also possible to use the corresponding polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols for the preparation of the polyesters.
  • suitable diols are ethylene glycol, butylene glycol, diethylene glycol,
  • Triethylene glycol Triethylene glycol, polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6) and isomers, neopentylglycol or hydroxypivalic acid neopentylglycol ester, the last three mentioned Compounds are preferred.
  • polyalkylene glycols such as polyethylene glycol, furthermore 1,2-propanediol, 1,3-propanediol, butanediol (1,3), butanediol (1,4), hexanediol (1,6) and isomers, neopentylglycol or hydroxypivalic acid neopentylglycol ester, the last three mentioned Compounds are preferred.
  • polyols having a functionality of 3 proportionally for example trimethylolpropane, glycerol, erythritol, pentaerythritol, trimethylolbenzene or trishydroxyethyl isocyanurate.
  • Suitable dicarboxylic acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, cyclohexanedicarboxylic acid, adipic acid, azelaic acid, sebacic acid, glutaric acid, tetrachlorophthalic acid, maleic acid,
  • Anhydrides of these acids are also useful, as far as they exist. As a result, for the purposes of the present invention, the anhydrides are encompassed by the term "acid”. It is also possible to use monocarboxylic acids, such as benzoic acid and hexanecarboxylic acid, provided that the average functionality of the polyol is> 2. Saturated aliphatic or aromatic acids are preferred, such as adipic acid or isophthalic acid. As polycarboxylic acid which may optionally be used in smaller amounts, trimellitic acid may be mentioned here.
  • Hydroxycarboxylic acids which can be used as reactants in the preparation of a hydroxyl-terminated polyester polyol include hydroxycaproic acid, hydroxybutyric acid, hydroxydecanoic acid, hydroxystearic acid and the like.
  • Suitable lactones are, for example, e-caprolactone, butyrolactone and their homologs.
  • polyester polyols b) based on butanediol and / or neopentyl glycol and / or hexanediol and / or ethylene glycol and / or diethylene glycol with adipic acid and / or phthalic acid and / or isophthalic acid.
  • Particularly preferred are polyester polyols b) based on butanediol and / or neopentyl glycol and / or hexanediol with adipic acid and / or phthalic acid.
  • the candidate polycarbonate polyols are prepared by reaction of carbonic acid derivatives, e.g. Diphenyl carbonate, dimethyl carbonate or phosgene with diols available.
  • diols come e.g. Ethylene glycol, 1,2- and 1,3-propanediol, 1,3- and 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, neopentyl glycol, 1,4-bishydroxymethylcyclohexane, 2-methyl-1, 3-propanediol, 2,2,4-trimethylpentanediol-1, 3, dipropylene glycol, polypropylene glycols, dibutylene glycol, polybutylene glycols, bisphenol A, tetrabromobisphenol A, but also
  • the diol component contains from 40 to 100% by weight of 1,6-hexanediol and / or hexanediol derivatives, preferably those having in addition to terminal OH groups ether or ester groups, e.g. Products obtained by reacting 1 mole of hexanediol with at least 1 mole, preferably 1 to 2 moles of ⁇ -caprolactone or by etherification of hexanediol with itself to di- or Trihexylenglykol. Polyether-polycarbonate polyols can also be used.
  • polycarbonate polyols b) based on dimethyl carbonate and hexanediol and / or butanediol and / or ⁇ -caprolactone Preference is given to polycarbonate polyols based on dimethyl carbonate and hexanediol and / or ⁇ -caprolactone. Very particular preference is given to polycarbonate polyols based on dimethyl carbonate and hexanediol and / or ⁇ -caprolactone.
  • polyester polyols are particularly preferred.
  • the low molecular weight polyols c) which may optionally be used to build up the polyurethane resins generally cause stiffening and / or branching of the polymer chain.
  • the molecular weight is preferably between 62 and 200 and its functionality is preferably 2 to 3.
  • Suitable polyols c) may contain aliphatic, alicyclic or aromatic groups.
  • the low molecular weight polyols having up to about 20 carbon atoms per molecule, such as ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-butylene glycol, cyclo- hexanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, hydroquinone dihydroxyethyl ether, bisphenol A (2,2-bis (4-hydroxyphenyl) propane), hydrogenated bisphenol A (2,2-bis (4-hydroxycyclohexyl) propane) and the like Mixtures, as well as trimethylolpropane, glycerol or pentaerythritol.
  • ethylene glycol diethylene glycol, triethylene glycol, 1, 2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,3-
  • ester diols for example ⁇ -hydroxybutyl- ⁇ -hydroxycaproic acid ester, ⁇ -hydroxyhexyl- ⁇ -hydroxybutyric acid ester, adipic acid ( ⁇ -hydroxyethyl) ester or terephthalic acid bis ( ⁇ -hydroxyethyl) ester.
  • Suitable nonionic hydrophilicizing compounds d) are e.g. Polyoxyalkylene ethers containing at least one hydroxy or amino group. These polyethers contain from 30% by weight to 100% by weight of building blocks derived from ethylene oxide. In question, linear polyethers have a functionality between 1 and 2, but also compounds of general formula (I),
  • R 1 and R 2 are each independently a divalent aliphatic, cycloaliphatic or aromatic radical having 1 to 18 C atoms, which may be interrupted by oxygen and / or nitrogen atoms, mean, and
  • R 3 is an alkoxy-terminated polyethylene oxide radical.
  • Nonionically hydrophilicizing compounds d) are, for example, also monohydric, on average 5 to 70, preferably 7 to 55 ethylene oxide units per molecule having Polyalkylenoxidpolyetheralkohole, as they are accessible in a conventional manner by alkoxylation of suitable starter molecules (eg in Ulimann's Encyclopedia of the technical Chemistry, 4th Edition, Volume 19, Verlag Chemie, Weinheim pp. 31-38).
  • starter molecules are saturated monoalcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, sec-butanol, the isomers pentanols, hexanols, octanols and nonanols, n-decanol, n-dodecanol, n-tetradecanol , Hexadecanol, n-octadecanol, cyclohexanol, the isomeric methylcyclohexanols or hydroxymethylcyclohexane, 3-ethyl-3-hydroxymethyloxetane or tetrahydrofurfuryl alcohol, diethylene glycol monoalkyl ethers such as diethylene glycol monobutyl ether, unsaturated alcohols such as allyl alcohol, 1,1-dimethylallyl alcohol or oleic alcohol,
  • Alcohols such as benzyl alcohol, anisalcohol or cinnamyl alcohol, secondary monoamines such as dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, bis (2-ethylhexyl) amine, N-methyl- and N-ethylcyclohexylamine or dicyclohexylamine and heterocyclic secondary amines such as morpholine, pyrrolidine, Piperidine or 1H-pyrazole.
  • Preferred starter molecules are saturated monoalcohols. Particularly preferred
  • Diethylene glycol monobutyl ether used as a starter molecule.
  • Alkylene oxides which are suitable for the alkoxylation reaction are, in particular, ethylene oxide and propylene oxide, which can be used in any desired order or even as a mixture in the alkoxylation reaction.
  • the molar mass M n of these building blocks is 300 g / mol to 6000 g / mol, preferably 500 g / mol to 4000 g / mol and particularly preferably 750 g / mol to 3000 g / mol with a functionality of 1.
  • Suitable such nonionically hydrophilicizing, monfunktionelle compounds d) are for example monofunctional alkoxypolyethylene glycols such as Methoxypolyethy- (MPEG Carbowax ® 2000 or methoxy PEG-40, molecular weight range 1800 to
  • MPEG Carbowax ® 2000, LB 25 or Jeffamine ® M 2070th Particularly preferred are MPEG Carbowax ® 2000 or LB 25th
  • Component e) contains potentially ionic groups, which may be either cationic or anionic in nature.
  • Cationic, anionic or nonionic dispersing compounds are those containing, for example, sulfonium, ammonium, phosphonium, carboxylate, sulfonate, phosphonate groups or the groups which can be converted into the abovementioned groups by salt formation ( potentially ionic groups) or Contain polyether groups and can be incorporated by existing isocyanate-reactive groups in the macromolecules.
  • suitable isocyanate-reactive groups are hydroxyl and amine groups.
  • Suitable ionic or potentially ionic compounds e) are e.g. Mono- and dihydroxycarboxylic acids, mono- and diaminocarboxylic acids, mono- and dihydroxysulfonic acids,
  • Mono- and diaminosulfonic acids and mono- and dihydroxyphosphonic acids or mono- and diaminophosphonic acids and their salts such as dimethylolpropionic acid, dimethylolbutyric acid, hydroxypivalic acid, N- (2-aminoethyl) - ⁇ -alanm, 2- (2-aminoethylamino) -ethane sulfonic acid, ethylenediamine-propyl- or butylsulfonic acid, 1,2- or 1,3-propylenediamine-.beta.-ethylsulfonic acid, malic acid, citric acid, glycolic acid, lactic acid, glycine, alanine, taurine, lysine, 3,5-diaminobenzoic acid, an addition product of IPDI and acrylic acid (EP-A 0 916 647, Example 1) and its alkali metal and / or ammonium salts; the adduct of sodium bisulfite with buten
  • Preferred ionic or potential ionic compounds are those which have carboxy or carboxylate and / or sulfonate groups and / or ammonium groups and have a functionality of 1.9 to 2.1.
  • Particularly preferred ionic compounds have an amine functionality of from 1.9 to 2.1 and contain sulfonate groups as ionic or potentially ionic groups, such as the salts of N- (2-
  • the polyamines f) used for chain extension preferably have a functionality between 1 and 2 and are e.g. Di- or polyamines as well as hydrazides, e.g. Ethylenediamine, 1,2- and 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, isophoronediamine,
  • component f) are in principle also compounds into consideration, which contain active hydrogen with respect to NCO groups of different reactivity, such as compounds which have not only a primary amino group but also secondary amino groups or in addition to an amino group (primary or secondary) OH groups.
  • Examples of this are primary / secondary amines, such as 3-amino-1-methylaminopropane, 3-amino-1-ethylaminopropane, 3-amino-1-cyclohexylaminopropane, 3-amino-1-methylaminobutane, furthermore alkanolamines, such as N-aminoethylethanolamine, ethanolamine, 3 Aminopropanol or neopentanolamine.
  • Diethanolamine and / or hydrazine and / or isophoronediamine (IPDA) and / or ethylenediamine are preferred. Particularly preferred are hydrazine and / or isophoronediamine and / or ethylenediamine. Very particularly preferred is a mixture of hydrazine and IPDA.
  • Suitable compounds g) are isocyanate-reactive polyepoxide compounds having an epoxy functionality between 2 and 4 and an isocyanate-reactive functionality between 1 and 2, preferably with an epoxide functionality between 2 and 4 and an isocyanate-reactive functionality of 1, particularly preferably with an epoxide functionality of 2 and an isocyanate-reactive functionality of 1.
  • hydroxyfunktione- Ie Polyepoxiditatien such as Glycerol diglycidyl ether, 1,4-bis (oxiran-2-yloxy) butan-2-ol, l, 5-bis (oxiran-2-ylmethoxy) -pentan-2-ol, 1- (oxiran-2-ylmethoxy) -6- (oxiran-2-yloxy) hexan-2-ol, 1- (oxiran-2-ylmethoxy) -6- (oxiran-2-yloxy) heptan-2-ol, 1- (oxiran-2-ylmethoxy) -6- (oxiran-2-yloxy) octan-2-ol, 1- (oxiran-2-ylmethoxy) -6- (oxiran-2-yloxy) nonan-2-ol, 1- (oxiran-2-ylmethoxy) -6- (oxiran-2-yloxy) decan-2-ol 1, 3-di (oxiran-2-yl) -propan
  • the amount of component g) to be used in the polyurethane-polyurea dispersion according to the invention varies depending on the application.
  • 2K system are preferably 0.5 to 15 wt .-%, more preferably
  • component g 3 to 12 wt .-% of component g) are used.
  • PU dispersions for the preparation of the PU dispersions according to the invention, it is possible to use all processes known from the prior art, such as e.g. Prepolymer mixing method, acetone method or Schmelzdipergiervon can be used.
  • the PU dispersion is preferably prepared by the acetone process.
  • aqueous polyurethane-polyurea dispersions which comprises first reacting the components a), b), c), d), e) and g) with an isopropoxide.
  • cyanate and epoxy groups-containing polyurethane prepolymer is prepared and this chain extended in a further step with NH 2 - and NH-functional components e) and f) and is converted into the aqueous phase.
  • the components b), c), d), e) and g) which may have no primary or secondary amino groups and the polyisocyanate component a) for the preparation of an isocyanate functional Polyurethane prepolymer completely or partially and optionally diluted with a water-miscible but isocyanate-inert solvent and heated to temperatures in the range of 50 to 120 0 C.
  • the catalysts known in polyurethane chemistry can be used. Preference is given to dibutyltin dilaurate.
  • Suitable solvents are the usual aliphatic, ketofunctional solvents, e.g. Acetone, butanone, which can be added not only at the beginning of the preparation, but possibly also in parts later. Preference is given to acetone or butanone.
  • the molar ratio of isocyanate groups to isocyanate-reactive groups is 1.0 to 3.5, preferably 1.1 to 3.0, particularly preferably 1.1 to 2.5.
  • NH 2 - and NH-functional components e) and f) are reacted with the remaining isocyanate and epoxide groups.
  • This chain extension / termination can be carried out either in a solvent before dispersing, during dispersion or in water after dispersion.
  • the chain extension is preferably carried out in water before dispersion. If compounds corresponding to the definition of e) and f) with NH 2 or NH groups are used for chain extension, the chain extension of the prepolymers preferably takes place before the dispersion.
  • the degree of chain extension ie the equivalent ratio of NCO-reactive groups of the compounds used for chain extension to free NCO groups of the prepolymer, is between 40 and 100%, preferably between 60 and 100%, particularly preferably between 70 and 100%.
  • the amine components e) and f) can be used individually or in mixtures in a form diluted with water or solvents in the process according to the invention, wherein in principle any sequence of addition is possible.
  • the diluent content is preferably 70 to 95% by weight.
  • the preparation of the polyurethaneurea dispersion according to the invention from the prepolymers takes place after the chain extension.
  • the dissolved and chain-extended polyurethane polymer is optionally sheared under high shear, such as, e.g. thick
  • the dispersing water is stirred to the prepolymer solutions.
  • the water is added to the dissolved prepolymer.
  • the solvent still present in the dispersions after the dispersion step is then usually removed by distillation. A removal already during the dispersion is also possible.
  • the solids content of the polyurethane polyurea dispersion according to the invention is between 20 to 70 wt .-%, preferably 30 to 65 wt .-% and particularly preferably between 35 to 62 wt .-%.
  • Another object of the invention is the use of the polyurethane-polyurea dispersions of the invention for the preparation of coating compositions for wood, plastic, metal, glass, textiles, leather, paper and fibers such. Glass fibers, plastic fibers and graphite fibers, preferably for the production of textile coatings.
  • the dispersions according to the invention can be brought to self-crosslinking thermally (1K system) or with epoxide-reactive and / or isocyanate-reactive polyfunctional ones
  • the invention relates to the use of the aqueous polyurethane-polyurea dispersions according to the invention for the preparation of thermally self-crosslinking IK systems.
  • aqueous polyurethane-polyurea dispersions according to the invention for the preparation of 2-component systems.
  • the 2-component systems comprising the polyurethane-polyurea dispersions according to the invention contain water-soluble or water-dispersible crosslinkers, such as hydrophilic polyisocyanates, polyamines, polyepoxides or melamines.
  • aqueous coating compositions comprising the polyurethane-polyurea dispersions according to the invention may contain auxiliaries and additives as further component.
  • These may be co-binders, thickeners, adhesives, lubricants, wetting additives, dyes, light and aging inhibitors, pigments, leveling agents, antistatic agents, UV absorbers, film-forming aids, defoamers or plasticizers, as well as light and aging inhibitors.
  • the polyurethane-polyurea dispersions of the invention can be used as a component in water-based coatings for coating surfaces.
  • the polyurethane-polyurea dispersions according to the invention are mixed with other components, e.g. polyester-based, polyurethane-based, polyurethane-polyacrylate-based, polyacrylate-based, polyether-based, polyester-polyacrylate-based, alkyd-resin-based, polymer-based, polyamide-imide-based or aqueous dispersions
  • the preparation of the coating can be carried out by the different spraying methods such as air pressure, airless or electrostatic spraying using single or optionally two-component spray systems.
  • the paints and coating compositions containing the polyurethane polyurea invention are described in detail below.
  • dispersions can also be applied by other methods, for example by brushing, rolling, spraying, dipping, spraying, printing or knife coating. Examples:
  • Desmodur I IPDI, isophorone diisocyanate (Bayer MaterialScience AG, DE).
  • Desmodur ® H HDI, 1, 6-hexamethylene diisocyanate (Bayer MaterialScience AG, DE).
  • IPDA isophoronediamine (Bayer MaterialScience AG, DE).
  • AAS diaminosulfonate, 45% in water, H 2 N-CH 2 -CH 2 -NH-CH 2 -CH 2 -SO 3 Na (Bayer MaterialScience AG, DE).
  • GDGE glycerol diglycidyl ether, CAS [27043-36-3] (Sigma-Aldrich, DE)
  • Bayhydur® ® 3100 Hydrophilic aliphatic polyisocyanate based on 1,6-hexamethylene diisocyanate having an NCO content of 17.4% (Bayer Material Science AG, DE).
  • Imprafix ® HS-C alkylamine (Bayer MaterialScience AG, DE).
  • a release paper is inserted in front of the rear roller.
  • a feeler gauge adjusts the distance between the paper and the front roller. This distance corresponds to the film thickness (wet) of the resulting coating and can be adjusted to the desired coverage of each stroke.
  • the coating is also possible consecutively in several strokes.
  • the products are poured onto the nip between the paper and the front roll after the viscosity has been adjusted by adding anionic acrylic polymer to 4500 mPa ⁇ s;
  • the release paper is pulled vertically downwards, forming the corresponding film on the paper. If several strokes are applied, each individual stroke is dried and the paper is inserted again.
  • the solids contents were determined according to DIN-EN ISO 3251.
  • NCO contents were determined volumetrically in accordance with DIN EN ISO 11909, unless expressly stated otherwise.
  • the free films were swollen in ethyl acetate at room temperature for 24 h, and the volume change of the film piece after swelling was determined by means of a ruler.
  • a 0.1-0.2 mm thick film is punched out in a size of 50X20 mm and stored for 2 hours in ethyl acetate at room temperature. The calculation of the volume swelling is made assuming that the change is proportional in all of the dimensions.
  • the film storage under hydrolysis takes place according to DIN EN 12280-3.
  • the mood of the mechanics of these film samples is carried out after 24 h storage under standard climatic conditions (20 0 C and 65% humidity) according to DIN 53504.
  • the determination of the mechanical film properties takes place after 30 minutes. Drying at 150 ° C.
  • ⁇ ⁇ , breaking elongation in%
  • O n ⁇ x tensile strength in MPa.
  • Example 2 The procedure of Example 1 is used, but there are 241 g of the polyester PE
  • Example 217 g of the polyester PE 170 HN with 47.8 GDGE are used.
  • the result is an aqueous dispersion having a solids content of 39.2% with a pH of 6.6 and an average particle size of 340 nm.
  • the Product is dispersed in 590 g of water and then the acetone is distilled off at 120 mbar at 40 ° C.
  • the result is an aqueous dispersion having a solids content of 40.0% with a pH of 6.5 and an average particle size of 350 nm.
  • Example 5 (counterexample, with ethylhexanol instead of isocyanate-reactive polyepoxide)
  • the free films were prepared as described.
  • the crosslinking agent Bayhydur 3100 ® or Imprafix ® HS-C were mixed with stirring in the dispersions and in turn generates the free films each 3 wt%.
  • the films were then mechanically characterized and the swelling determined in ethyl acetate.
  • the polyurethanes according to the invention have lower degrees of swelling and thus a higher degree of crosslinking in comparison with the counterparts.
  • the dispersions thus have a higher molecular weight even after the preparation and can still be postcrosslinked thermally, the degrees of swelling decreasing as the amount of the polyepoxide compound increases.
  • the polyurethanes according to the invention are both more isocyanate-reactive and amine-reactive, from which it can be deduced that both epoxy, hydroxy and amine groups must be present.
  • dispersions according to the invention have a significantly higher stability to hydrolysis, the stability to hydrolysis increasing with increasing proportion of the polyepoxide compound.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Abstract

La présente invention concerne des dispersions de polyuréthane-urée aqueuses comportant des groupes fonctionnels incorporés, ainsi que des produits de revêtement fabriqués à partir de ces dispersions, un procédé de préparation desdites dispersions et leur utilisation pour fabriquer des produits de revêtement.
PCT/EP2010/000801 2009-02-19 2010-02-10 Dispersions de polyuréthane-polyurée fonctionnalisées WO2010094417A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US13/147,254 US8513334B2 (en) 2009-02-19 2010-02-10 Functionalized polyurethane polyurea dispersions
CN201080008282.XA CN102325816B (zh) 2009-02-19 2010-02-10 官能化聚氨酯聚脲分散体
ES10703236T ES2400415T3 (es) 2009-02-19 2010-02-10 Dispersiones de poliuretanopoliureas funcionalizadas
EP10703236A EP2398835B1 (fr) 2009-02-19 2010-02-10 Dispersions de polyuréthane-polyurée fonctionnalisées
JP2011550454A JP5542846B2 (ja) 2009-02-19 2010-02-10 官能化されたポリウレタンポリ尿素分散液

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EP09002307A EP2221330A1 (fr) 2009-02-19 2009-02-19 Dispersions de poly-résine de polyuréthane fonctionnalisées
EP09002307.8 2009-02-19

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DE102007059090A1 (de) * 2007-12-07 2009-06-10 Benecke-Kaliko Ag Polymermischung
JP6231495B2 (ja) * 2012-01-25 2017-11-15 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ 布地被覆用ポリウレタン分散体
EP2861684B1 (fr) 2012-06-15 2016-03-30 3M Innovative Properties Company Composition durcissible formant de polyurée, son procédé de préparation et article composite
EP3250621A4 (fr) 2015-01-30 2018-01-17 Hewlett-Packard Development Company, L.P. Dispersion de liant à base de polyuréthane
CN107922762B (zh) 2015-10-28 2021-02-05 惠普发展公司，有限责任合伙企业 基于可辐射固化聚氨酯的粘合剂分散体
CN109312172A (zh) * 2016-06-10 2019-02-05 凯密特尔有限责任公司 在水相中稳定化的基料
EP3504258B1 (fr) 2016-08-25 2022-10-05 Stepan Company Compositions de polymère polyester-époxyde
ES2940660T3 (es) * 2017-03-02 2023-05-10 Stepan Co Composiciones poliméricas de poliéster-epóxido modificado con isocianato
EP3601406B1 (fr) 2017-03-31 2021-04-14 Stepan Company Compositions de polymère polyéther-époxyde
JP7105177B2 (ja) * 2018-11-09 2022-07-22 大日精化工業株式会社 ポリウレタン樹脂水分散体、塗料、フィルム構成体、及び構造物
EP3898758A1 (fr) 2018-12-19 2021-10-27 Stepan Company Compositions adhésives à un seul constituant
US10907004B2 (en) 2018-12-28 2021-02-02 Industrial Technology Research Institute Waterborne polyurethane and preparation method thereof
FR3109583B1 (fr) * 2020-04-28 2022-07-29 Arkema France Dispersion aqueuse de poly(ester-uréthane) ou de poly(ester-urée-uréthane)

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WO2010094417A8 (fr) 2011-07-14
JP2012518064A (ja) 2012-08-09
TWI565726B (zh) 2017-01-11
TW201041922A (en) 2010-12-01
CN102325816A (zh) 2012-01-18
ES2400415T3 (es) 2013-04-09
EP2221330A1 (fr) 2010-08-25
EP2398835A1 (fr) 2011-12-28
EP2398835B1 (fr) 2012-12-19
JP5542846B2 (ja) 2014-07-09
US20110288204A1 (en) 2011-11-24
CN102325816B (zh) 2014-04-30
US8513334B2 (en) 2013-08-20

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